JPH0788201B2 - Sterilizing / deodorizing composition and sterilizing / deodorizing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sterilizing / deodorizing composition and a sterilizing / deodorizing method. More specifically, the present invention relates to a sterilizing / deodorizing composition and a sterilizing / deodorizing method capable of sterilizing and deodorizing various objects existing in an atmosphere by generating chlorine dioxide in a gaseous state.

(B) Conventional Technology Chlorine dioxide (ClO ₂ ) is known to have a sterilizing action, a deodorizing action, a bleaching action and the like due to its strong oxidizing ability. However, chlorine dioxide has the drawbacks that it is difficult to store because it is a gas body and that a gas generator is required.

Therefore, conventionally, two solid compounds that can react to generate chlorine dioxide in water were used, and chlorine dioxide was generated on the spot by adding them to water at the time of use to act on various objects in the atmosphere. A sterilizing / deodorizing method is known. Then, as a drug for carrying out such a method, for example, a proposal of a solid composition in which hypochlorite and chlorite are combined (Japanese Patent Publication No. 61-19561) or a combination of hypochlorite and citric acid There is a proposal to combine such an organic acid.

(C) Problems to be Solved by the Invention However, the conventional chlorine dioxide generating solid composition as described above has a low chlorine dioxide generating efficiency, or
When added to water, the chlorine dioxide generation reaction rapidly proceeded, and there was a tendency that the chlorine dioxide generation ability of the prepared solution decreased in a short time (within one day). As a result, although the sterilization and deodorizing ability is exhibited immediately after preparation, the effect does not last and the application requiring the sterilization and deodorizing effect for a relatively long period of time, for example, a refrigerator, a fruit storage box. However, it was not satisfactory for sterilizing and deodorizing applications such as fish boxes.

In particular, in refrigerators and fruit storage boxes, ClO ₂ is usually added to the atmosphere in an amount of 0.0001 to 0.05 for sterilization and air purification.
% (1 to 500 ppm), and it is desired that the concentration be maintained for a certain period of time, and that the concentration be decreased after this period and not remain in the system from the viewpoint of effect and toxicity. However, when the conventional solid composition for chlorine dioxide generation is used, the period in which a large amount of chlorine dioxide is initially generated and the above concentration is maintained is extremely short, and especially sterilization for several days to several weeks is required. There was a big problem in the use in the above target systems where deodorization is desired.

The present invention has been made under such circumstances, in particular, a sterilization / deodorization method capable of stably generating an optimum concentration of chlorine dioxide from water and enabling sterilization / deodorization for a longer period than ever before. And to provide a composition suitable therefor.

(D) Means and Actions for Solving the Problems Thus, according to the present invention, an alkali metal or alkaline earth metal salt of chlorous acid and the following formula (I): M ₂ S ₂ O _n (I) (In the formula, n is a real number of 4 to 8, M is an alkali metal or ammonium) and a sulfur-containing oxygen acid easily water-soluble salt is reacted in an aqueous medium to release chlorine dioxide gas. There is provided a sterilization / deodorization method characterized by performing sterilization / deodorization with chlorine dioxide gas.

Examples of the alkali metal or alkaline earth metal salt of chlorous acid used in the present invention include sodium chlorite NaClO ₂ , potassium chlorite KClO ₂ , calcium chlorite Ca (Cl
O _{2) 2,} magnesium chlorite Mg (ClO _{2) 2} and the like, they may be used as a mixture. Of these, it is preferable to use NaClO ₂ or KClO ₂ .

On the other hand, specific examples of the easily water-soluble salt of sulfur-containing oxygen acid used in the present invention, Na ₂ S ₂ O ₄ , K ₂ S ₂ O ₅ , K ₂ S ₂ O ₈ , Na ₂ S ₂ O ₆ ,
(NH ₄ ) ₂ S ₂ O _{8 and the} like. Other than this, for example, 2KHSO ₅ ·
Double salts such as KHSO ₄ and K ₂ SO ₄ are also included. Of course, these may also be mixed and used. Of these, it is preferable to use K ₂ S ₂ O ₅ or K ₂ S ₂ O ₈ .

In the sterilization / deodorization method of the present invention, the chlorite and the sulfur-containing oxygenate are added to an aqueous medium such as water. Although the liquidity of the aqueous medium is not particularly limited, it is usually suitable to use neutral to acidic water. At this time, the amounts of both components added are adjusted so that they react with each other to generate chlorine dioxide gas having a desired concentration. Usually of chlorite
0.0001 to 10% by weight, and an amount of sulfur-containing oxyacid salt (usually 0.0001 to 10% by weight) sufficient to generate a desired concentration of chlorine dioxide by reacting with this chlorite in an aqueous medium. It can be added. And more specifically, the use ratio of chlorite and sulfur-containing oxygenates is preferably 1: 0.01 to 10 by weight ratio, and by adjusting this ratio, the generation concentration and the generation period are controlled. You can also

Such a chlorine dioxide generating liquid uses a solid sterilizing / deodorizing composition of the present invention containing both components prepared by mixing in advance corresponding to the above-mentioned concentration and ratio, and using this in an appropriate amount of an aqueous medium. It is convenient and preferable to use by adding and dissolving. In such a sterilized / deodorized composition, a suitable inorganic carrier, a fragrance and a slight reaction accelerator may be contained.

Furthermore, a gelling agent such as a water-absorbing polymer may be contained, and a gel-like or jelly-like chlorine dioxide-generating liquid can be prepared by this.

The sterilization / deodorization method of the present invention stores an aqueous medium such as water in an appropriate container, and dissolves both components in the aqueous medium to generate chlorine dioxide. An appropriate number of odors can be arranged in or near the intended object. Alternatively, the reaction may be carried out in a gas-permeable plastic bag to generate chlorine dioxide, and an appropriate number of the bags may be similarly arranged in or near the object. In particular, a gas-permeable outer bag uses a bag having a double structure in which the composition for sterilization / deodorization of the present invention and an easily tearable inner bag containing an aqueous medium are built in, and the inner bag is manually put into use during use. It is convenient in terms of handling that the above-mentioned components are dissolved in an aqueous medium to generate chlorine dioxide, and the generated chlorine dioxide is released to the outside through an outer bag.

In the present invention, the reaction between the chlorite and the sulfur-containing oxyacid salt is smoothly carried out at room temperature, whereby chlorine dioxide is generated. Then, this chlorine dioxide generation reaction proceeds not relatively rapidly as in the conventional case but relatively mildly. Therefore, chlorine dioxide is generated stably for a long period of time,
A stable sterilization and deodorizing effect is exhibited for a long period of from about 1 day to 2 weeks, and in some cases up to about 1 month, and chlorine dioxide is prevented from remaining after use.

(E) Examples Example 1 By mixing 0.1 g of sodium chlorite (purity 80%) and 1.0 g of potassium peroxodisulfate (K ₂ S ₂ O ₈ ) to sterilize the mixed powder of the present invention A deodorant composition was prepared.

This composition was added and dissolved in distilled water to prepare a chlorine dioxide generating liquid in which 0.1% by weight of sodium chlorite and 1% by weight of potassium peroxodisulfate were dissolved.

In order to investigate the chlorine dioxide generation characteristics of this generated liquid, the dissolved chlorine dioxide gas concentration in the generated liquid under open (about 25 ° C)
It measured with time using the tripolar polarographic diaphragm type electrode device shown below.

Working electrode: Gold Counter electrode: Platinum Reference electrode: Silver / silver chloride Diaphragm: Porous (pore size 25 μm) polypropylene Buffer solution: Sodium acetate buffer pH4.0 Setting electrode: + 0.55V Detector: ECD detector by Diox Recorder: Type 3066 manufactured by Yokogawa Electric Co., Ltd. The results are shown in FIG. Note that Fig. 1 (e)
Indicates that according to the conventional method, sodium chlorite 0.1
This is due to a chlorine dioxide generating solution in which a weight% of the solution is dissolved in an aqueous citric acid solution (pH 4.0).

Thus, the concentration of chlorine dioxide generated peaks at 40 ppm, and is maintained at a concentration of 5 ppm or more until about 6 days after the preparation, and it is clear that chlorine dioxide is released to the outside at an optimum concentration for a long period of time.

Example 2 An aqueous solution containing 0.1% by weight of sodium chlorite and 0.1% by weight of potassium peroxodisulfate was prepared according to Example 1.
The chlorine dioxide evolution characteristics were investigated.

The results are shown in FIG. As described above, the concentration of chlorine dioxide generated is stable at about 10 ppm, and it can be seen that the optimum concentration of chlorine dioxide is released for a long period of up to about 2 weeks.

Example 3 In accordance with Example 1, an aqueous solution containing 0.1% by weight of sodium chlorite and 0.01% by weight of potassium peroxodisulfate was prepared, and the chlorine dioxide generation characteristics were examined.

This result is as shown in FIG.
It can be seen that 3 ppm of chlorine dioxide is stably released for about 1 week.

Further, in any of the above examples, no chlorine dioxide remained after the reaction was completed.

As shown in such an embodiment, the sterilization
The deodorant composition has a chlorine dioxide generating ability for a long period of time as compared with the conventional one, and by changing the concentration ratio of the chlorite and the sulfur-containing oxygenates, the chlorine dioxide generating period and It can be seen that the release concentration can be adjusted. Therefore, it can be seen that the chlorine dioxide releasing ability can be adjusted depending on the application and the period of action.

(F) Effect of the Invention According to the present invention, chlorine dioxide can be released into the atmosphere for a long period of time as compared with the prior art, and the release period can be adjusted according to the purpose. Also, the residual chlorine dioxide is prevented from remaining after the above period has elapsed.

[Brief description of drawings]

FIG. 1 is a graph showing a chlorine dioxide generation characteristic when the method of the present invention is carried out together with a comparative example.

Claims (2)

[Claims] 1. An alkali metal or alkaline earth metal salt of chlorous acid and the following formula (I): M ₂ S ₂ O _n (I) (wherein, n is a real number of 4 to 8 and M is A sterilizing / deodorizing composition comprising a readily water-soluble salt of a sulfur-containing oxygen acid represented by (indicating an alkali metal or ammonium). 2. Dioxide is obtained by reacting an alkali metal or alkaline earth metal salt of chlorous acid with a water-soluble salt of a sulfur-containing oxygen-oxygen acid represented by the formula (I) of claim 1 in an aqueous medium. A sterilization / deodorization method characterized by releasing chlorine gas and sterilizing / deodorizing with this chlorine dioxide gas.